Hair bleaching compositions and process

ABSTRACT

HAIR BLEACHING COMPOSITIONS CONTAINING CERTAIN DICARBONYL COMPOUNDS AND A PEROXYGEN COMPOUND AS ESSENTIAL COMPONENTS, SAID COMPOSITIONS HAVING A PH IN A RANGE OF FROM ABOUT 8 TO 11, AND HAIR BLEACHING PROCESS.

United States Patent ()flice 3,816,615 Patented June 11, 1974 3,816,615 HAIR BLEACHING COMPOSITIONS AND PROCESS Eugene Zeliren and Richard B. Knohl, Wyoming, Ohio,

assignors to The Procter & Gamble Company, Cincinnati, Ohio No Drawing. Filed Aug. 5, 1971, Ser. No. 169,538

. Int. Cl. A61k 7/12 U.S. Cl. 424.-62 17 Claims ABSTRACT OF THE DISCLOSURE Hair bleaching compositions containing certain dicarbonyl compounds and a peroxygen compound as essential components, said compositions having a pH in a range of from about 8 to about 11, and hair bleaching process.

BACKGROUND OF THE INVENTION the like in that hair bleaching compositions, in addition to oxidizing and destroying the colored melanin of the hair, must be suitable for use in contact with the human skin and must not damage the hair excessively. Further- I more, since hair bleaches are a member of the class of materials known as cosmetics, it is desirable that they be aesthetically acceptable to the user. Finally, it is desirable that a hair bleaching composition remove the melanin coloration from the hair as quickly as possible, both for the sake of convenience and to help prevent untoward damage to the hair and irritation to the skin and scalp. Most current bleaching systems require exposure to the hair for periods of from about 2 to hours, depending upon the desired degree of bleaching. Such long periods of exposure frequently result in irritation to the skin and some damage to the hair.

Hair bleaches commonly consist of a peroxide oxidizing agent, bleach enhancing agents, and a variety of additional cosmetic and bleach stabilizing agents. Oxidizing agents such as the various hypochlorites and halogenated cyanuric acid compounds suitable for use on hard surfaces and in fabric bleaching are not suitable for use on hair since they are too damaging and too irritating to the skin. Peroxide bleaches used on hair must be activated, this being accomplished by the use of an activating agent to adjust the pH to a basic range. The most common material for adjusting the pH of peroxide hair bleaching compositions is an aqueous solution of ammonia, commonly referred to as ammonium hydroxide.

In addition to ammonium hydroxide, a variety of other activating and/or enhancing agents have been suggested for use in hair bleaching compositions. US. Pat. 2,283,- 350, granted May 19, 1942 to N. Baum, discloses the use of aliphatic amines and hydroxyaliphatic amines as substitutes for ammonium hydroxide in hair bleaching compositions. Moreover, US. application Ser. No. 129,554, filed Mar. 30, 1971 by Knohl and Zelfren, entitled Hair Bleaching Compositions and Process, discloses hair bleaches containing arginine and various arginine-containing proteins; Another U.S. application, Ser. No. 129,555, filed Mar. 30, 1971 by Knohl and Zelfren, entitled Hair Bleaching Composition and Process, now abandoned discloses hair bleaches containing quanidine compounds which eliminate the need for ammonium hydroxide thereby providing a bleaching composition having essentially no odor or skin irritation which is attributable to ammonium hydroxide. The use of guanidine compounds in place of ammonium hydroxide is a preferred embodiment of the present invention and will be discussed more fully hereinafter. This patent and these applications are incorporated herein by reference.

As discussed briefly above, current bleaching systems and processes inevitably cause some damage to the hair and this damage is usually attributed to the oxidation of cystine bonds in the hair polymer. This cystine oxidation damage is increased by higher peroxide concentrations in the bleach and by longer contact times of said bleach with the hair. It has been unexpectedly found that the use of the dicarbonyl compounds of the present invention result in superior bleaching characteristics, while permitting the use of significantly lower amounts of bleaching activitties thereby causing less skin irritation and hair damage. Further, the dicarbonyl compounds of the present invention result in considerably shorter bleaching times, further diminishing skin irritation and hair damage.

THE PRIOR ART A variety of activating and/or enhancing agents for peroxygen compounds are known in the art. See, for example, U.S. 3,338,839 to MacKellar et al., which issued on Aug. 29, 1967. Other compositions are disclosed in US. 2,955,905 to Davies et al., which issued Oct. 11, 1960; and US. 3,177,148 to Bright et al., which issued on Apr. 6, 1965. However, the prior art does not disclose the dicarbonyl compounds of the present invention or their use in hair bleaching compositions.

Accordingly, it is an object of the present invention to provide improved peroxygen bleaching compositions containing certain dicarbonyl compounds of the type hereinafter disclosed.

It is another object of the present invention to provide hair bleaching compositions which are faster acting and less damaging than known hair bleaches.

It is yet another object of the present invention to provide improved bleaching compositions which are more aesthetically pleasing. These and other objects are obtained by the present invention as will become apparent from the following disclosure.

SUMMARY OF THE INVENTION The bleaching compositions of the present invention comprise:

(A) from about 0.1% to about 10% by weight of a dicarbonyl compound of the formula:

l u n l? n-o-o-R, or RGCH2CR wherein each I and II compound, each R is selected from the group consisting of hydrogen; hydroxy; alkyl groups of from about 1 to 4 carbon atoms; hydroxyalkyl groups of frornabout 1 to 4 carbon atoms; carboxyalkyl groups of from about 1 to 4 carbon atoms;

aryl groups containing from about 6 to about 12 carbon atoms, for example, phenyl, biphenyl and naphthyl; and aralkyl groups of from about 6 to about 14 carbon atoms, for example,; benzyl, paraethylphenyl, and 2-phenylethyl; and each R is selected from the group consisting of hydrogen; hydroxy; alkyl groups of from 1 to about 4 carbon atoms; hydroxyalkyl groups of from about 1 to about 4 carbon atoms; carboxyalkyl groups of from' about 1 to about 4carbon atoms; aryl groups containing from about 6 to about 12 carbon atoms, for example, phenyl, biphenyl and naphthyl; aralkyl groups of from about 6 to about 14 carbon atoms, for example, benzyl, paraethylphenyl, and Z-phenylethyl; alkoxy containing groups of from about 1 to about 3 carbon atoms; and M-O groups wherein M is NHfi, an alkali metal or alkaline earth metal,

3 v for example, Na K M'g and Ca++; and where a in each-I andII compound at least-one carbonyl group must be a ketone or aldehyde group. In addition, in each I and 11 compound, R and R may be connected to form a cyclic compound, for example, 1,2-cyclohexanedione and ,1,3-.cyclohexanedione; (B) from about 1% to. about 10% by weight'of a watersoluble peroxygen compound-which yields hydrogen peroxide insolution; and (C) from about to about 98.9%. of inert ingredients such as liquids, for example, water; lower alcohols, for example, ethylene glycol, propylene glycol, 1,3-propropanediol, ethanol, isopropyl alcohol and glycerine; and mixtures thereof, and solids such as starch, NaCl, Na SO amorphous silicates, and the like, said bleaching compositions having a pH of from about 8 to about 11 in water at use concentrations.

In addition to the above essential components, the bleaching compositions of the present invention may contain as a preferred embodiment certain bleach enhancing agents more fully defined hereinafter.

In addition to the above compounds, the bleaching compositions of the present invention may also contain additional agents such as buffers, thickeners, perfumes and other minor ingredients to make the composition more aesthetically pleasing.

In addition, this invention encompasses a process for bleaching hair, especially growing humain hair, which comprises contacting said hair with a composition comprising as essential components a peroxygen compound and a dicarbonyl compound, the pH of said composition being in the range of from about 8 to about 11.

DETAILED DESCRIPTION OF THE INVENTION It has been surprisingly found that certain dicarbonyl compounds such as those discussed more fully hereinafter, when combined with a peroxygen compound, wherein the pH of the composition is from about 8 to about 11, preferably from about 9 to about 10, markedly improve the speed of bleaching and in the preferred bleaching compositions described hereinafter make possible the use of about A the peroxygen concentration currently used while greatly decreasing the time necessary for bleaching. Heretofore, it was necessary to bleach the hair for about 2 to about hours, depending upon the degree of bleaching desired. The present invention makes it possible to get desirable bleaching action in from about /2 hour to about 2 hours, depending upon the level of bleaching desired. The lower concentration of peroxygen compound plus the greatly decreased time necessary for bleaching to be accomplshed results in less skin irritation and less damage to the hair. In addition, it results in a more aesthetically pleasing and convenient composition.

While not intending to be restricted by theory, it is hypothesized that the dicarbonyl compounds react with the peroxygen compound to form a compound which penetrates the hair shaft more rapidly and/or causes an increased reaction rate of melanin bleaching. Whatever the reason for the improved hair bleaching activity of the present compositions, the improvement is not attributable merely to the pH, but is related to the presence of the dicarbonyl compounds.

' The dicarbonyl compounds used herein include those having the formula: i

where in each I and II compound, each R is selected from the group consisting of hydrogen; hydroxy; alkyl groups of from about 1 to 4 carbon atoms; hydroxyalkyl groups of from about 1 to 4 carbon atoms; carboxyalkyl groups of from about 1 to 4 carbon atoms; aryl groups containing from about 6 to 12 carbon atoms, for example, phenyl,

biphenyl and naphthyl; and aralkyl groups of from about 6 to about 14 carbon atoms, for example, benzy1,paraethylphenyl, and 2-phenyletl1yl; and each R is selected from the group consisting of hydrogen; hydroxy; alkyl groups of from 1 to about 4 carbon atoms; hydroxyalkyl groups of from about 1 to about 4 carbon atoms carboxyalkyl groups of from about 1 to about 4 carbon atoms; aryl groups containing from about 610 about 12 carbon atoms,.for example, phenyl, biphenyl and naphthyl; and aralkyl groups of from about 6 to about 14 carbon atoms,'for example, benzyl, paraethylphenyl, and 2-phenylethyl; alkoxy containing groups of from about 1 to about 3 carbon atoms; and MO groups wherein M is NH an alkali metal or alkaline earth metal, for example, Na K+, Mg++ and Ca++; and where in each I and 11 compound at least one carbonyl group must be a ketone or aldehyde group. In each compound I and II, R and R may be connected to form a cyclic compound, for example, 1,2-cyclohexanedione, and 1,3-cyclohexanedione. The term aralkyl as used herein means any alkyl and any aryl combination within the defined limits, e.g., alkaryl, alkaralkyl, etc.

Examples of compounds of formula I include: 2,3- butanedione, sodium pyruvate, 2,3-pentanedione, benzil,

3,4-hexanedione, 1,2-cyclohexanedione, potassium pyru vate, ammonium pyruvate, ethyl pyruvate, magnesium pyruvate, a-ketoglutaric acid dimethyl ester and 2,3- hexanedione, pyruvic acid, m-ketopropanal, a-ketobutyn aldehyde, calcium 3-biphenyl pyruvate, paraethylbenzil, ethyl phenylpyruvate, methyl naphthylpyruvate, calcium a-retobutyrate, sodium a-keto-fl-phenylbutyrate, a-ketoglutaric acid, 1,5-dihydroxy-2,3pentanedione, l-naphthyl- Z-biphenylethanedione, and l-paraethylphenyl- 1,4-diphenyl-2,3-butanedione, 2,3-butanedione and sodium pyruvate are most preferred.

Examples of compounds of formula II, include: 1,3; cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, pketoglutaric acid dimethyl ester, ethyl acetoacetate, acetoacetic acid, methyl acetoacetate, 2,4pentanedione, 2,4- hexanedione, 3-ketopentanal, 3-ketohexanal, 1,3-cycloheptanedione, propioacetic acid, sodium, ammonium and potassium acetoacetates, sodium and potassium propioacefates, and magnesium and calcium acetoacetates, fl-ketoglutaric acid, sodium naphthoacetate, methyl phenylacetoacetate, methyl paraphenylbenzoacetate, 3,4-diketohexa noic acid, l-naphthyl- 3-biphenyl-1,3-propanedion'e, 1- paraethylphenyl 5 phenyl 1,3-pentanedione, 1,5-dihydroxy 2,4 pentanedione, a-benzoacet ophenone, and lphenyl-3-propio-2-propanone. Most preferred are 1,3

cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and fi-ketoglutaric acid dimethyl ester.

The dicarbonyl compounds are used in the bleaching compositions of this invention at concentrations from about 0.1% to about 10%, preferably from about 0.8% to about 4% by weight of the total composition in the form to be applied to the hair. If a compound of the formula I is used, the preferred concentration is from about 0.8% to about 4%. If a compound of the formula II is used, the preferred concentration is from about 0.8% to about 3%.

Suitable water-soluble peroxygen compounds for ,use in the compositions and process of the present invention include: hydrogen peroxide, any of the water-solublealkali metal peroxides, e.g., sodium and potassium peroxide, etc.; alkaline earth metal peroxides; peroxide-complexes such as the water-soluble addition compounds of materials such as urea and guanidine with hydrogen perox-' ide, e.g., urea peroxide, guanidine peroxide, and the like;

organic peracids; organic hydroperoxides; and inorganic peroxygen salts such asperborates, such as sodium per-. borate, persilicates, percarbonates, perphosphates and perpyrophosphates.

Preferred peroxygen compounds for use in the compositions of the present invention are those which yield hydrogen peroxide in solution. Such compounds include hydrogen peroxide, the water-soluble alkali metal peroxides, the alkaline earth metal peroxides, the water-soluble peroxide-complexes such as urea peroxide and the like, theperborates, such as sodium perborate, and the percarbonatesysuch as, potassium percarbonate. Most preferred for use in the compositions of the present invention are hydrogen peroxide, urea peroxide, and sodium perborate.

The peroxygen component of the bleaches described herein usually comprises from about 1% to about by weight of the total composition. A peroxygen concentration of from about 2% to about 6% by weight is most preferred.

In addition to the components described, the compositions of the present invention may also contain as a preferred embodiment one or more of certain bleach enhancing agents in amounts of from about 0.1% to about 45% by weight. One example of such a bleach enhancing agent is 'amrn'onium' hydroxide which can be present in amounts of from about 0.1% to about 25%, preferably from about 2% to about 10%.

Other bleach enhancing agents which may be utilized in the present invention include agents such as ammonium peroxydisulfate or alkali metal peroxydisulfates or any of the other common peroxygen salts commonly used in hair bleaching compositions such as the ammonium or alkali metal peroxydiphosphates described in South African Patent Application 692,638, published Nov. 26, 1969, to R. Cohen. Mixtures of any of the foregoing enhancing agents are also suitable. These enhancing agents are preferably' each used at a concentration of from about 1% to about 10%, most preferably from about 3% to about 8% by weight. Ammonium peroxydisulfate, the potassium andsodium peroxydisulfates, and potassium peroxydiphosphate are preferred agents of this type.

"Another example of preferred bleach enhancing agents for use in the compositions of the present invention includes certain guanidine compounds.

The guanidine compounds used herein include guanidine and'it s basic derivatives, as Well as the reaction products of these compounds with an acid, i.e., guanidinium salts. Such "basic compounds and salts are referred to collectively herein as guanidine compounds. Compounds such as guanidine, monoalkyl-guanidines, dialkyl-, trialkyl-, andtetraalkyl-guanidines having alkyl substituents on each amine nitrogen atom, aryl-guanidines of the same type, especially 'N,N'-diphenylguanidines, and the like all can be suitably employed per se or neutralized with acids of'the type hereinafter disclosed to form soluble guanidiniurn salts which are suitably employed in the bleaching compositions of'this invention. For example, guanidine, N phenylguanidine, N methylguanidine, N butylguanidine, N ,N.' diphenylguanidine, N-phenyl-N-hexylguanidine, N hydroxyethylguanidine, N,N,N',N' tetraethylguanidine, N,N-dihydroxymethylguanidine, N,N-diphenylN-hydroxybutylguanidine, and the like can be used per se or can be treated with an acid of the type hereinafter disclosed to prepare guanidinium salts suitable and preferred for use herein. Guanidine and the substituted guanidine compounds are commercially available materials.

Acids which can be reacted with guanidine and the basic derivatives thereof to provide guanidinium salts suitable for use in the bleaching compositions of this invention include those acids having anions which are compatible with peroxides, especially hydrogen peroxide. For example, mineral acids such as hydrochloric acid, phosphoric acid, carbonic acid, sulfuric acid, nitric acid, and the organic acids such as formic acid, acetic acid, lauric acid, chloroacetic acid and the like are all suitable for this use. Acids containing metallo-anions and strongly reducing anions, e.g., chromicacid and, hydrogen thiocyanate, are not suitable herein in that these anions react with the peroxide.

Reaction of the aforementioned guanidine and derivatives thereof with the exemplary acids in the appropriate amounts yields the guanidinium salts useful herein. For example, guanidinium chloride, guanidinium carbonate, guanidinium sulfate, N-methylguanidinium sulfate, N- decylguanidinium hydrochloride, N-methoxyguanidinium phosphate, N hydroxymethyl N hydroxyethylguanidinium carbonate, N-phenylguanidinum carbonate, N'phenylguanidinium chloride, 'N-phenyl-N'-hexylguanidinium hydrochloride, guanidinum phosphate, guanidinium pyrophosphate, guanidinium nitrate, guanidinium acetate, guanidinium chloroacetate and the like, are suitable for use in the compositions of this invention. The carbonates and phosphates are preferred for this purpose in that they are self-buffering. Guanidinium chloride, guanidinium phosphate and guanidinium carbonate are especially preferred for use herein in amounts of from about 2% to about 10% by weight.

As noted heretofore the various bleach enhancing agents can be used singly or in mixtures thereof. For the purpose of the present invention, a preferred guanidinium compound or combination with a preferred ammonium peroxydisulfate or an alkali metal peroxydisulfate is most preferred. For example, a preferred composition embodying the present invention comprises:

(A) from about 0.8% to about 4% by weight of a dicarbonyl compound selected from the group consisting of sodium pyruvate, 2,3-butanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and ,3- ketoglutaric acid dimethyl ester;

(B) from about 2% to about 6% by weight of a watersoluble peroxygen compound selected from the group consisting of hydrogen peroxide, sodium perborate, and urea peroxide;

(C) from about 3% to about 8% by weight of a bleach enhancing agent selected from the group consisting of ammonium peroxydisulfate, potassium peroxydisulfate, sodium peroxydisulfate, potassium peroxydiphosphate, and mixtures thereof;

(D) from about 2% to about 10% by weight of a bleach enhancing agent selected from the group consisting of guanidinium carbonate, guanidinium chloride and guanidinium phosphate and mixtures thereof; and

(E) balance, water.

As noted hereinabove, peroxygen containing hair bleaches are used in the basic pH range of from about 8 to about 11. During the course of the hair bleaching operation, the pH of the bleach solution will sometimes change; therefore, in a preferred embodiment of this invention, a buffer is included in the composition to maintain a relatively constant pH within the desired range. Any of the common peroxide-stable buffers suitable for use in the pH range from 8 to 11 can be used herein for this purpose, e.g., carbonates, Na HPO Na PO etc. Especially preferred herein are phosphate buffers, especially ortho-, meta-, and tripolyphosphate salts. While any of the common buffers are useful herein, the phosphate? buffer salts have the advantage that they are innocuous when applied to the skin, are eflicient buffers over-the pH range indicated, and stabilize the peroxide being used by preventing metal ion catalyzed peroxide decomposition.

Buffers such as the phosphates can be used at concentra tions from about 0.1% to about 5% by weight in the present compositions. When the carbonate and phosphate" salts of the guanidine compounds are used herein they act as their own pH buffers and maintain'the basicity of the bleaching composition within the optimal range. When such carbonate or phosphate salts are used herein, some additional base or buffer can be included to help maintain pH stability and to help stabilize the peroxygen compound.

Hair bleachingcompositions designed for use on'the head are difiicult to apply properly withoutthe use of thickeners. It is, therefore, desirable to include thickening agents in the herein-disclosed compositions to impart a creamy gel consistency thereto such that they are adapted for localized application. A variety of such thickening agents suitable for use with peroxide hair bleaching compositions are well known in the cosmetic arts and all such thickeners are useful in the present compositions. For example, sodium metasilicate is commonly used for this purpose as are various clays, carboxymethylcellulose compounds and the like. Thickeners can be used at concentrations from about 1% to about 5% of the bleaching compositions.

The present compositions can contain various other adducts to provide a more cosmetically acceptable prod uct. Such materials as perfumes, dyes, and the like can be added to the bleaching compositions detailed herein to provide a more pleasant cosmetic aspect. In addition, trace quantities of stabilizers such as the ethylenediaminetetraacetates, phosphates, citrates and the like may also be used.

Hair Bleaching Test A hair bleaching test was carried out as follows:

Hair switches were prepared by cutting small amounts from a commercial sample of brown virgin European hair and dipping the cut end in glue. Switches used herein were about six inches long and weighed from 1 to 2 grams. In the bleaching operation the switches were tied to a stirring rod and immersed in 50 ml. of freshly prepared bleaching solution for periods up to 60 minutes. The test compositions were those prepared in Examples I-IV below and in Table I. The control bleach comprised 6% by weight hydrogen peroxide containing 6% ammonium peroxydisulfate and about 3% ammonia supplied as 9% concentrated ammonium hydroxide. Estimates of bleaching activity were made visually by comparing the treated switch to a set of 30 standard switches sequentially number 1-30, with grade 1 being no bleaching and grade 30 being very extensive bleaching, and estimates of bleach damage were made tactilely. The test results indicate that the control system gives a color grade of 16. At the same time, the degree of damage in the five tests (control and first four examples below) were approximately equal, indicating that for a given degree of damage, the dicarbonyl containing compositions bleach more rapidly than the control bleach.

The following examples serve to illustrate the bleaching compositions of this invention but are not intended to be limiting thereof. In the examples, water is used as the common solvent for the components of the bleach compositions. Water can be replaced, in part, by up to about 50% by liquids such as the lower alcohols, e.g., ethylene glycol, propylene glycol, 1,3-propanediol, ethanol, isopropyl alcohol, glycerine and mixtures thereof. The bleaches herein are applied to hair for periods of one minute to four hours, depending upon the degree of bleaching desired. A preferred time is between and 45 minutes.

EXAMPLES I AND II Ingredient Amount Amount Guanidinium chloride, g 4. 5 4. 5 Sodium pyrophosphate, g.- 2. 0 2. 0 Ammonium peroxydisuli'ate, g 3. 0 3.0 Hydrogen peroxide (30% by weight aqueous solution), g 5.0 5. 0 Sodium 1.0 1,3-cyclo exanedione,g 0.5 Water 1 To 50 ml. total volume.

8 and 4% sodium pyrophosphate, sodium pyruvate in Example I at 2%, and 1,3-cyclohexanedione in Example II at 1%. The pH of the solutions was 9.2. These bleaching compositions were successfully used to bleach human hair in the manner detailed in the Hair Bleaching Test, above. A color grade of 23 was obtained for Example I and a grade of 22 for Example H.

EXAMPLES III AND IV 1 To 50 ml. total volume.

The above bleaching compositions were prepared by dissolving the guanidinium carbonate and the ammonium peroxydisulfate in about 30 ml. of water, adding the hydrogen peroxide, followed by the respective dicarbonyl compound, and diluting the resulting solution to 50 ml. The final concentration in this bleach was 3% hydrogen peroxide, 6% ammonium peroxydisulfate, 9% guanidinium carbonate, 2% sodium pyruvate, in Example III and 1% 1,3-cyclohexanedione in Example IV. The pH was 9.2. The self-buffering bleaching composition prepared in this manner was successfully used to bleach human hair in the Hair Bleaching Test, above. A color grade of 24 was obtained for the composition of Example III and a color grade of 23 for the composition of Example IV.

EXAIWPLES V AND VI 1 50 m1. total volume.

The above bleaching compositions are prepared by dissolving the N-methylguanidinium carbonate and the potassium peroxydisulfate in about 30 ml. of water, adding the hydrogen peroxide, and then the respective dicarbonyl compounds and diluting the resulting solution to 50 ml. The final concentration in these bleaching solutions is 3% hydrogen peroxide, 6 ammonium peroxydisulfate, 9% N-methylguanidinium carbonate, 2% 2,3-butanedione of Example V, and 1% 1,3-cyclohexanedione of Example VI. The pH of the solutions is about 9.2. This self-buffering, non-odorous bleaching composition is applied to human hair and rapidly bleaches it. The pH is adjusted to 8.0 with HCl and equivalent results are secured.

Compositions are prepared in accordance with those prepared in Examples V and VI above except that the 2,3-butanedione of Example V is replaced by an equivalent amount of sodium pyruvate, 2,3-pentanedione, benzil, 3,4-hexanedione, 1,2-cyclohexanedione, potassium pyruvate, ammonium pyruvate, ethyl pyruvate, magnesium pyruvate, a-ketoglutaric acid dimethyl ester, 2,3-hexanedione, pyruvic acid, a-ketoproponal, a-ketobutyraldehyde, calcium 3-biphenyl pyruvate, paraethylbenzil, ethyl phenylpyruvate, methyl naphthylpyruvate, calcium a-ketobutyrate, sodium a-keto-B-phenylbutyrate, a-ketoglutaric acid, 1,5-dihydroxy-2,3-pentanedione, l-naphthyl- Z-biphenylethanedione and the 1,3-cyclohexanedione of Example VI is replaced by an equivalent amount of 5,5-dimethyl 1,3 cyclohexanedione, B-ketoglutaric acid dimethyl ester, ethyl acetoacetate, acetoacetic acid, methyl acetoacetate, 2,4-pentanedione, 2,4-hexanedione, 3-ketopentanal, 3 ketohexanal 1,3 cycloheptanedione, propioacetic acid, sodium, ammonium, and potassium acetoacetates, sodium and potassium propioacetates, and magnesium and calcium acetoacetates, fl-ketoglutaric acid, sodium naphthoacetate, methyl phenylacetoacetate, methyl paraphenylbenzoacetate, 3,4-diketohexanoic acid, l-naphthyl-3-biphenyl 1,3 propanedione, 1 paraethylphenyl-S-phenyl-1,3-pentanedione, 1,5-dihydroxy-2,4-pentanedione, a-benzoacetophenone, and 1-phenyl-3-propio- 2-propanone. In each instance, equivalent results are obtained in that odorless bleaching compositions having shortened bleaching times and less damaging effects on growing hair are obtained.

In the above compositions of Examples V and VI, the N-methylguanidinium carbonate is replaced by an equivalent amount of N-decylguanidinium carbonate, N-hydroxyethylguanidinium carbonate, N-phenylguanidinium carbonate, N,N' bis (hydroxymethyl)guanidinium carbonate, N-phenyl-N-ethylguanidinium carbonate, N,N,N', N'-tetraethylguanidinium carbonate, and N-paramethoxyphenylguanidinium carbonate, respectively, and equivalent results are secured in that the odorless bleaching compositions thereby obtained rapidly bleach growing human hair.

EXAMPLES VII AND VIII Thiekened bleaching compositions Percent Percent Ingredient (wt.) (wt.)

Guanldinium carbonate 20 20 onium peroxydisuliate 10 10 liyidrggen peroxide (30% by weight aqueous solu- 8 8 on Sodium matnsilinnto 2 2 Sodium pyruvate 2 5 6-dirnethyl-l,3-cyclohexanedione 1 ntor Balance Balance The above bleaching compositions are prepared by dissolving the guanidinium carbonate, the ammonium peroxydisulfate and the hydrogen peroxide in about 50 ml. of water, adding the respective dicarbonyl compounds, and adding the sodium metasilicate to provide a thickened solution. The bleaching compositions so obtained are essentially odorless and rapidly bleach growing human hair.

Compositions'of the type prepared in Examples VII and VIII above are prepared except that the sodium pyruvate of Example VII is replaced by an equivalent amount, of 2,3-butanedione, 2,3-pentanedione, benzil,

3,4-hexanedione, 1,2-cyclohexanedione, potassium pyruvate, ammonium pyruvate, ethyl pyruvate, magnesium pyruvate, a-ketoglutaric acid dimethyl ester, 2,3-hexanedione, pyruvic acid, wketopropanal, u-lretobutyraldehyde," calcium 3-biphenyl tanedione, 2,4-hexanedione, 3-ketopentanal, 3-ketohexanal, 1,3-cycloheptanedione, propioacetic acid, sodium, ammonium and potassium acetoacetates, sodium and potassium propioacetates, and magnesium and calcium "acetoacetates, fi-ketoglutaric acid, sodium naphthoacetate, methyl phenylacetoacetate, methyl paraphenylbenzoacetate, 3,4-diketohexanoic acid, 1-naphthyl-3-biphenyl-1,3-

propanedione, l-paraethylphenyl 5 phenyl-1,3-pentanedione, l,5-dihydroxy-2,4-pentanedione, a benzoacetophe- 'none, and 1-phenyl-3-propio-2 propanone.

In the above compositions, the guanidinium carbonate is replaced by an equivalent amount of guanidinium phosphate, guanidinium nitrate, guanidinium bicarbonate,

N-methyl-guanidinium acetate, and N-phenylguanidinium laurate; respectively. The equivalent hair bleaching compositions so obtained rapidly and safely bleach human EXAMPLES IX AND K Dry peroxide bleaching composition Percent Percent Ingredient (wt.)

Guanidinlum carbonate 40 Sodium perborate 5 Potassium peroxydisullate. 0. 5 Ammonium peroxydisuliat 0.; 2 4

Sodium metasilicate Ten grams of either of the above compositions is mixed with ml. of water and provides a thickened, buffered bleaching composition which rapidly and safely bleaches hair. The compositions are essentially odorless.

In the above compositions, each of the following modifications is made:

The sodium perborate is replaced by an equivalent amount of potassium peroxide, potassium percarbonate, and urea peroxide complex, respectively, and the resulting bleach compositions thereby secured are applied to human hair for periods from about 10 minutes to about 2 hours, depending upon the degree of lightness desired, and effectively bleach said hair.

The potassium peroxydisulfate is replaced by an equivalent amount of a 1:1 (wt.) mixture of ammonium peroxydisulfate and ammonium peroxydiphosphate and equivalent bleaching compositions are secured.

The potassium metasilicate is replaced by an equivalent amount of sodium carboxymethylcellulose and a thickened bleach is thereby secured.

The sodium tripolyphosphate is replaced by an equivalent amount of sodium hydrogen phosphate and trisodium phosphate (1:1 wt.) and buffered bleaches are secured.

The sodium perborate is replaced by sodium peroxide at concentrations of 1% and 10% by weight, respectively, and hair bleaching compositions are thereby provided. The sodium perborate in the above compositions is replaced by urea peroxide at concentrations of 1% and 10% by weight, respectively, and odorless hair bleaches are thereby secured.

The guanidinium carbonate is replaced by an equivalent amount of guanidine, N-methyl-guanidine, N-decylguanidine, N,N,N',N'-tetraphenylguanidine, N,N,N',N-

-tetrabutylguanidine, N-hydroxymethylguanidine, N-chlorophenyl N hydroxybutylguanidine and N-phenyl-N- naphthyl N'-methyl-N'-hydroxymethylguanidine, respectively, and the compositions are buiiered at pH 9 with 5% by weight of a sodium hydrogen phosphate-trisodium phosphate bufier and equivalent bleaches are thereby secured.

The sodium pyruvate of Example IX is replaced by an equivalent amount of 2,3-butanedione, 2,3-pentanedione benzil, 3,4-hexanedione, 1,2-cyclohexanedione, potassium pyruvate, ammonium pyruvate, ethyl pyruvate, magnenesium pyruvate, a ketoglutaric acid dimethyl ester, 2,3- hexanedione, pyruvic acid, u-ketopropanal, m-ketobutyraldehyde, calcium 3-biphenyl pyruvate, paraethylbenzil, ethyl phenylpyruvate, methyl naphthylpyruvate, calcium a-ketobutyrate, sodium a-keto-B-phenylbutyrate, a-keto glutaric acid, 1,5-dihydroxy2,3-pentanedione, l-paraethylphenyl 1,4-diphenyl-2,3-butanedione, and the 1,3-cyclohexanedione of Example X is replaced by an equivalent amount of 5,5-dimethyl-1,3-cyclohexanedione, fi-ketoglutaric acid dimethyl ester, ethyl acetoacetate, acetoacetic acid,methyl acetoacetate, 2,4-pentanedione, 2,4-hexanedione, 3-ketopentanal, 3-ketohexanal, 1,3-cycloheptanedione, propioacetic acid, sodium, ammonium and potassium acetoacetates, sodium and potassium propioacetates, magnesium and calcium acetoacetates, p-ketoglutaric acid, sodium naphthoacetate, methyl phenylacetoacetate, methyl paraphenylbenzoacetate, 3,4-diketohexanoic acid, 1-naphthyl-3-biphenyl-1,3-propanedione, l-paraethylphenyl S-phenyl-1,3-pentanedione, 1,5-dihydroxy-2,4-pentanedione, a benzoacetophenone, and l-phenyl-S-propio-2- propanone.

Additional examples within the scope of the present invention are listed below in Table I. In all cases, a 2 g. hair switch was immersed in a 50 ml. test solution as in the Hair Bleaching Test above.

TABLE I.--EXAMPLES XI-XXVII Percent Quantdinium Sodium H1O: (NH4)2S2O5 carbonate NH=+ pyruvate 1. 3-cyclohexanedione Color grade Protamine phosphate cacewmwmzowwecwwwxowww Control.

Control used in hair bleaching test.

In each instance the bleaching compositions of the present invention exhibited superior bleaching characteristics with less hair damage.

Hair bleaching products are typically marketed in kit form, i.e., a package comprising an individually packaged oxidizing component and an individually packaged bleaching assistant. In an embodiment of this invention said oxidizing component consists of a stabilized aqueous solution of a peroxygen compound as detailed herein, most generally aqueous hydrogen peroxide in an amount such that the final concentration of the composition for use on the hair is from about 1% to about 10% by weight, and said bleaching assistant component comprises a dicarbonyl compound of the present invention, a bleaching accelerator of the type hereinbefore detailed and a guanidine compound or salt thereof, of the type hereinabove detailed. The components are mixed by the user immediately prior to application to the hair. An example of such kit is as follows:

A hair bleaching kit is assembled comprising a single package including therein: (1) a 4 oz. bottle of hydrogen peroxide (6% by weight H O and (2) a foil packet containing a bleaching assistant, said assistant consisting of 4 g. of ammonium peroxydisulfate, g. of guanidinium carbonate; and (3) a 1 oz. bottle containing 4 g. of sodium pyruvate, 2 g. of sodium carboxymethylcellulose and 10 g. of starch. The bleaching assistant is admixed with the hydrogen peroxide and the contents of the 1 oz. bottle are added thereto. The resulting solution is applied to the hair and bleaches it.

In the above composition the sodium pyruvate is re placed by an equivalent amount of 2,3-butanedione, or 2 g. of 1,3-cyclohexanedione, 5,5 dimethyl-1,3-cyclohexanedione and fi-ketoglutaric acid dimethyl ester and equivalent results are obtained.

In the above composition the guanidinium carbonate is replaced by an equivalent amount of guanidinium phosphate, guanidinium chloride, N-methylguanidinium phos phate, N-methylguanidinium chloride and N-phenylguanidinium carbonate and equivalent results are secured.

In the above composition the 6% aqueous hydrogen peroxide solution is replaced by an equivalent volume of 3% hydrogen peroxide solution and substantially equivalent results are secured.

In the above composition the guanidinium carbonate is replaced by 0.1 g. of N-methylguam'dinium chloride, 0.5 g. of guanidine, 1.0 g. of N-methylguanidine, 10 g.

(A) from about 0.1% to about 10% by weight dicarbonyl compound of the formula:

ll ll II II R-C-C-Rr or R-C-CHr-C-Rl where in formulas I and II, R is selected from the; group consisting of hydrogen; hydroxy; alkyl groups of from about 1 to 4 carbon atoms; hydroxyal lgyl groups of from about 1 to 4 carbon atoms; carb'oxy alkyl groups of from about 1 to 4 carbon atoms; aryl: groups containing from about 6 to about 12 carbon atoms; and aralkyl groups of from about 6 to about 14 carbon atoms; and each R is selected from the group consisting of hydrogen; hydroxy; alkyl groups of from 1 to about 4 carbon atoms; hydroxyalkyl groups of from about 1 to about 4' carbon atoms; carboxyalkyl groups of from'about 1 to about 4 ca1'-' bon atoms; aryl groups containing from about 6 to about 12 carbon atoms; ar'alkyl groups of from about 6 to about 14 carbon atoms; alkoxy containing groups of from about 1 to about'3 carbon atoms; M- O' groups wherein M is NHfi, an alkali metal or alkaline earth metal; and where in each I and '11 compound at least one carbonyl group must be a ketone or aldehyde; or R'and R may be connected to form a cyclic compound having 6 or 7 carbon the cyclic group; t (B) from about 1% to about 10% by weight'of 'a water-soluble peroxygen compound which yields hydrogen peroxide in solution; and

(C) from about 0% to about 98.9% of inert dilue'nts; said bleaching composition having a pH-of from about 8 to about 11 when used in-an aqueous medium. i

atoms 2. The composition of claim 1 wherein the dicarbonyl acid, 1,S-dihydroxy-2,3-pentanedione, 1 naphthyl-2-bi.-i

phenylethanedione, 1 paraethylphenyl-1,4-diphenyl-2,3- butanedione, 1,3-cyclohexanedione, 5,5 dimethyl-1,3-cyclohexanedione, fl-ketoglutaric acid dimethyl ester, ethyl acetoacetate, acetoacetic acid, methyl acetoacetate, 2,4- pentanedione, 2,4-hexanedione, 3-ketopentanal, 3 ketohexanal, 1,3-cycloheptanedione, p'ropioacetic acid, sodium acetoacetate, ammonium acetoacetate, potassium acetoacetate, sodium propioacetate, potassium propioacetate, magnesium acetoacetate, calcium acetoacetate, B-ketoglutaric acid, sodium naphthoacetate, methyl phenylacetoacetate, methyl paraphenylbenzoacetate, 3,4 diketohexanoic acid, 1 naphthyl-3-biphenyl-1,3-propanedione, 1- paraethylphenyl-S-phenyl 1,3 pentanedione, 1,5-dihydroxy-2,4-pentanedione, a benzoacetophenone, and 1- phenyl-3-propio-2-propanone.

3. The composition of claim 1 wherein the dicarbonyl compound is selected from the group consisting of sodium pyruvate, 2,3-butanedione, 1,3-cyclohexanedione, 5,5-dimethyl 1,3 cyclohexanedione, and fi-ketoglutaric acid dimethyl ester.

4. The composition of claim 1 wherein the water-soluble peroxygen compound is selected from the group consisting of hydrogen peroxide, alkali metal peroxide, sodium perborate, and urea peroxide.

5. The composition of claim 1 which contains from about 0.1% to about 45% by weight of one or more bleach enhancing agents in addition to said dicarbonyl compound.

6. The composition of claim 1 which contains, in addition, from about 0.1% to about 45% by weight of one or more additional bleach enhancing agents selected from the group consisting of guanidinium carbonate, guanidinium chloride, and guanidinium phosphate, ammonium hydroxide, ammonium peroxydisulfate, potassium peroxydisulfate, sodium peroxydisulfate, potassium peroxydiphosphate, and mixtures thereof.

7. The composition of claim 1 which contains, in addition, from about 0.1% to about 5% by weight of a peroxygen-compatible butter capable of maintaining a pH of from about 8 to about 11 in aqueous solution.

8. A hair bleaching composition according to claim comprising:

(A) from about 0.8% to about 4% by weight of a dicarbonyl compound selected from the group consisting of sodium pyruvate, 2,3-butanedione, 1,3-cyclohexanedione, 5,5 dimethyl-1,3-cyclohexanedione, and fl-ketoglutaric acid dimethyl ester;

(B) from about 2% to about 6% by weight of a water-soluble peroxygen compound selected from the group consisting of hydrogen peroxide, sodium perborate, and urea peroxide;

and which contains, in addition:

(C) from about 3% to about 8% by weight of a bleach enhancing agent selected from the group consisting of ammonium peroxydisulfate, potassium peroxydisulfate, sodium peroxydisulfate, potassium peroxydiphosphate, and mixtures thereof;

(D) from about 2% to about 10 %by weight of a bleach enhancing agent selected from the group consisting of guanidinium carbonate, guanidinium chloride and guanidinium phosphate and mixtures thereof; and

(E) balance, water.

9. The composition of claim 8 which contains, in addition, from about 0.1% to about 5% by weight of a peroxygen-compatible buffer capable of maintaining a pH of from about 8 to about 11 in aqueous solution.

10. A process for bleaching hair which comprises applying to the hair an effective amount of an aqueous hair bleaching composition which is suitable for use in contact with the human skin and which comprises:

(A) from about 0.1% to about 10% by weight of a dicarbonyl compound of the formula:

where in each formula I and II, R is selected from the group consisting of hydrogen; hydroxy; alkyl groups of from about 1 to 4 carbon atoms; hydroxyalkyl groups of from about 1 to 4 carbon atoms; carboxyalkyl groups of from about 1 to 4 carbon atoms; aryl groups containing from about 6 to about 12 carbon atoms; and aralkyl groups of from about 6 to about 14 carbon atoms; and each R is selected from the group consisting of hydrogen; hydroxy; alkyl groups of from 1 to about 4 carbon atoms; hydroxyalkyl groups of from about 1 to about 4 car-. bon atoms; carboxyalkyl groups of from about 1 to about 4 carbon atoms; aryl groups containing from about 6 to about 12 carbon atoms; aralkyl groups of from about 6 to about 14 carbon atoms; alkoxy containing groups of from about 1 to about 3 carbon atoms; M-O groups wherein M is NHfi, an alkali metal or alkaline earth metal; and where in each I and 11 compound at least one carbonyl group must be a ketone or aldehyde; or R and R may be connected to form a cyclic compound having 6 or 7 carbon atoms in the cyclic group;

(B) from about 1% to about 10% by weight of a water-soluble peroxygen compound; and

(C) from about 0% to about 98.9% of inert diluents,

said bleaching composition having a pH of from about 8 to about 11.

11. A process according to claim 10 wherein the dicarbonyl compound is selected from the group consisting of 2,3-butanedione, sodium pyruvate, 2,3-pentanedione, benzil, 3,4-hexanedione, 1,2 cyclohexanedione, potassium pyruvate, ammonium pyruvate, ethyl pyruvate, magnesium pyruvate, a-ketoglutaric acid dimethyl ester, 2,3-hexanedione, pyruvic acid, u-ketopropanal, a-ketobutyraldehyde, calcium S-biphenyl pyruvate,, paraethylbenzil, ethyl phenylpyruvate, methyl naphthylpyruvate, calcium u-ketobutyrate, sodium a-keto-p-phenylbutyrate, a-ketoglutaric acid, 1,S-dihydroxy-Z,3-pentanedione, l-naphthyl 2 biphenyl ethanedione, l-paraethylphenyl-1,4-diphenyl 2,3 butanedione, 1,3 cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, fl-ketoglutaric acid dimethyl ester, ethyl acetoacetoacetate, acetoacetic acid, methyl acetoacetate, 2,4- pentanedione, 2,4-hexanedione, 3 ketopentanal, 3-ketohexanal, 1,3-cycloheptanedione, propioacetic acid, sodium acetate, ammonium acetoacetate, potassium acetoacetate, sodium propioacetate, potassium, propioacetate, magnesium acetoacetate, calcium acetoacetate, fl-ketoglutaric acid, sodium naphthoacetate, methyl phenylacetoacetate, methyl paraphenylbenzoacetate, 3,4-diketohexanoic acid, 1-naphthyl-3-biphenyl-1,3-propanedione, l-paraethylphenyI-S-phenyl-1,3-pentanedione, 1,5-dihydroxy-2,4-pentanedione,a-benzoacetophenone, and 1-phenyl-3-propio-2-propanone.

12. A process according to claim 10 wherein the dicarbonyl compound is present in an amount of from about 0.8% to about 4% by weight and is selected from the group consisting of sodium pyruvate, 2,3-butanedione, 1,3- cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and fl-ketoglutaric acid dimethyl ester.

13. A process according to claim 10 wherein the watersoluble peroxygen compound is present in an amount of from about 2% to about 6% by weight and is selected from the group consisting of hydrogen peroxide, alkali metal peroxides, sodium perborate, and urea peroxide. 1

14. A process according to claim 10 wherein the bleaching composition contains from about 0.1% to about 45% by weight of one or more bleach enhancing agents in addition to said dicarbonyl compound.

15. A process according to claim 10 wherein the bleaching composition contains, in addition, a bleach enhancing 15 agent selected from the group consisting of guanidinium carbonate, guanidinium chloride, guanidinium phosphate, ammonium hydroxide, ammonium peroxydisulfate, potassium peroxydisulfate, sodium peroxydisulfate, potassium peroxydiphosphate, and mixtures thereof.

16. A process according to claim 10 wherein the bleaching composition contains, in addition, from about 0.1% to about 5% by weight of a peroxygencompatible buifer capable of maintaining a pH of from about 8 to about 11.

17. The composition of claim 1 which contains, in addition, from about 0.1% to about 45% by weight of an additional bleach enhancing agent selected from the group consisting of ammonium hydroxide, alkali metal peroxydisulfate, ammonium peroxydisulfate, alkali metal peroxydiphosphate, ammonium peroxydiphosphate, guanidine, guanidine compounds having alkyl substituents on each amine nitrogen atom, guanidine compounds having aryl substituents on each amine nitrogen atom, and water-soluble guanidinium salts.

References Cited UNITED STATES PATENTS ALBERT T. MEYERS, Primary Examiner D. R. ORE, Assistant Examiner US. or. X.R.

20 8111, 111.5; 252186; 424--Dig. 3

W050 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,816,615 Dated June 11, 1974 Inventor) Eugene Zeffren & Richard B. Knohl It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: "'1 Col. 2, line 14, "activitties" should read actives Col. 4, line 31, "d-retobutyrate" should read a'-ketobutyrate Col. 4, line 34, after phenizl-ZJ-butanedione, should read Col. 7, line 69, "peroxydisulfite" should read peroxydisulfate Col. 7 line 75 peroxydisulfiate" should read peroxydisulfate Col. 8, line 67, after "2-biphenylethanedione" should read and l-paraethylphenyl-fl,4-diphenyl-2,3-butanedione;

Col. 9, line 54, diphenyl-2,3-butanedione,'sho'uld'read and l-paraethylphenyll,4diphenyl2,3-butanedione; Col. 10, line 66, after l,5-dihydroxy-2,3-pentanedione," should read l-naphthyl-2biphenylethanedione, and

Col. 10, line 67, after "phenyll,4diphen,yl-2,3-butanedione",

should read -r vw v a Col. 14, line 50, "acetate" should read acetoacetate Col. 14, line 51, "potassium, propioacetate" should read potassium propioa'cetate Col. 15 line 8, "peroxygencompatible" should read peroxygen compatible Signed and sealed this 1st day of- October 1974.

(SEAL) Attst:

MCCOY M. GIBSON JR. I i v c., MARSHALL DANN Atrestmg Officer I Commissioner of Patents Po-wso UNITED STATES PATENT OFFICE QERTIHCATE 0F CORRECTEON Patent No. 3, 81.6 ,615 D t d June 11, 1974 lnventofls) Eugene Ze ffren & Richard B. Knohl It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

... I Col. 2, line 14, "activitties" should read actives Col. 4, line 31, "d retobu'tyrate" should read a-ketobutyrate Col. 4, line 34, after phenyl-2,3-butanedione, should read Col. 7, line 69, "peroxydisulfite" should read peroxydisulfate Col. 7, line '75 "peroxydisulfiate" should read peroxydisulfate Col. 8, line 67 after "2-biphenylethanedione should read and l-paraethylphenyL-ji,4-diphenyl-2,3butanedione; Col. 9 line 54, diphenyl-2 ,3-butanedio'ne',", should read and l-paraethylphenyl-l,4-diphenyl-2,3-butanedione; Col. 10, line 66, after "l,5dihydroxy-2,3-pentanedione," should read 1-naphthyl-2biphenylethanedione, and Col. 10, line 67, after "phenyll,4-diphenyl-2,3-butanedione",

" should read 1; --u 7 a a v Col. 14, line 50, acetate" should read acetoacetate Col. 14, line 51, "potassium, propioacetate" should read potassium propioacetate Col. 15, line 8, "peroxygencompatible" should read P P Ygen compatibl p sl ned and sealed this 1st d of. October 197,.

(SEAL) Attest:

MCCOY M. GIBSON JR. l 7 c0, MARSHALL DANN Attesrgmg Officer Commissioner of Patents 

